Determination of sulfoxide bond dissociation enthalpies of dibenzothiophene S-oxide derivatives with computational methods.

Photodeoxygenation of dibenzothiophene S-oxide (DBTO) has been suggested as a clean way to generate atomic oxygen in solution. Sulfoxide bond dissociation enthalpies (BDEs) are important to the quantum yield and mechanism of this photodeoxygenation. In this study, BDE of substituted DBTO molecules with various functional groups were determined using M062X/aug-cc-pV(T + d)Z and MP2/aug-cc-pV(T + d)Z levels of theory. The sulfoxide BDE was determined using an isodesmic reaction. The observed effect of substitution was that functional groups with negative σpara values (electron donating) strengthen the sulfoxide bond and that substituents with positive σpara values (electron withdrawing) weaken the sulfoxide bond. The Mulliken charge on sulfur for DBTO and the corresponding dibenzothiophene were identified as a suitable indicator of the predicted S-O BDE. Moreover, steric and hydrogen bonding interactions were found to affect sulfoxide BDE for certain functional groups when located at the 1 or 4 positions of the substituted DBTO. Copyright © 2014 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]